Fire-resistant resin

ABSTRACT

A liquid polymerizable material which may be used, for instance, for the coating of wood or other substrate, which material, when cured, is fire-resistant and protects the substrate. The material cures without application of heat and is formed from methyl methacrylate monomer, a hydroxy alkylacrylate or diacetone acrylamide monomer, a chlorinated hydrocarbon, an antimony compound, a zinc compound, a filler, and a catalyst-promoter system.

BACKGROUND OF THE INVENTION

The potential use of synthetic polymeric materials in the buildingconstruction industry has long been recognized. The low cost, ease ofhandling, and desirable maintenance characteristics, make plasticsobvious materials for use in the manufacture of building components suchas coatings, panels, and trim. One problem which has held back theprogress of polymer compositions in this area is that they are generallyquite flammable and, as thin coatings, they provide little fireprotection to substrates on which they are laminated. Furthermore, thecombustion of organic polymers usually generates billows of malodoroussmoke which not only hampers firefighting efforts but also turns evensmall fires into major problems. Additionally, the "kindling" effect ofthe burning polymers often elevates the flame temperature, therebyigniting articles which would not have been effected. Another problem isthat most polymers cure slowly, require addition of heat to cure, orrelease dangerous solvents during curing, all of which make manufacturedifficult. In the case of pre-polymerized materials the mechanicalfabrication requires very expensive molds and the like. One of the mostdesirable types of polymers are polyacrylates. Attempts have been madeto reduce the combustibility of these materials by adding"flame-proofing agents" such as chlorinated paraffin wax, tricresylphosphate and tris (2,3-dichloropropyl) phosphate (see British PatentNo. 1,157,436 to Norman Wilkins, 1969). Such a prior art material, asseen in Example 2, has a Flame Spread Rating (F.S.R.) of 100 asdetermined by the Steiner Tunnel Test (A.S.T.M. E84) (using anequivalent 2 ft. tunnel). An F.S.R. of 25 or below would be far moredesirable. These and other difficulties experienced with the prior artcompositions have been obviated in a novel manner by the presentinvention.

It is, therefore, an outstanding object of the invention to provide aliquid polymerizable composition which, after curing, is fire resistant.

A further object is to provide a bulk molding compound from which can bemolded fire-resistant articles that will not necessarily be attached toany substrate.

Another object of this invention is the provision of a liquidpolymerizable composition from which fire-resistant articles can befabricated.

A further object of the present invention is the provision of apolymeric composition which can be used as a coating not only to renderinexpensive substrates (such as construction-grade plywood) moreattractive, but also protect the substrate from both moisture and fire.

It is another object of the instant invention to provide a polymericcomposition which is non-burning and self-expanding, thereby forming athermal barrier when exposed to intense heat.

A still further object of the invention is the provision of a liquidpolymerizable composition which is applied to a substrate in liquidform, adhers well, increases in viscosity quickly, and cures at roomtemperature.

It is a further object of the invention to provide a polymericcomposition which gives off little or no smoke when exposed to flame andhas little objectionable smell when exposed to flames or when used inmanufacturing a product.

A further object of the invention is the provision of a buildingmaterial that changes from liquid to solid without the release ofsolvent or other objectionable volatile component.

A still further object is to provide a fire-resistant gel coat on areinforced fiberglass laminate having load-bearing capabilities, such asbuilding components, boats, car and truck bodies and the like.

With the foregoing and other objects in view, which will appear as thedescription proceeds, the invention resides in the combination andarrangement of steps and the details of the composition hereinafterdescribed and claimed, it being understood that changes in the preciseembodiment of the invention herein disclosed may be made within thescope of what is claimed without departing from the spirit of theinvention.

SUMMARY OF THE INVENTION

In general, this invention involves a liquid polymerizable compositionof the acrylate type which is fire resistant and can be used as acoating to protect substrates which are not fire resistant. Thecomposition cures to a hard surface which is wear and moistureresistant, but which is non-burning and self-expanding when exposed tointense heat. These latter properties cause the thin coating to expandinto a thick layer of thermal insulation which protects the substrate.

The mixture contains thermoplastic components, a flame-retardingcomponent, a blowing or puffing component, and fillers. Morespecifically the mixture includes methyl methacrylate monomer, a hydroxyalkylacrylate or diacetone acrylamide monomer, an antimony compound, azinc compound, a chlorinated hydrocarbon, and a catalyst-promotersystem.

BRIEF DESCRIPTION OF THE DRAWING

The character of the invention, however, may be best understood byreference to one of its structural forms, as illustrated by theaccompanying drawing, in which is shown a structural panel embodying theprinciples of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

In order to place the characteristic of the composition that will bedescribed in this disclosure in proper perspective, an example of apractical use is shown in the drawing. A wall panel 10 is shown with amagnified cutaway of the layers with which it is fabricated. The baselayer or substrate 11 is three-fourths inch construction-grade plywood.To this substrate is applied a thin tiecoat 12 of a polyester resin.This coat seals the plywood and provides a uniform surface for furtherlayers. While the tiecoat is still tacky, the fire-retardant coat 13 isapplied. This coat is applied with a thickness of about one-sixteenthinch. In addition, a cosmetic coat 14, which in the preferred embodimentconsists of a sprinkling of small stones, can be applied to enhance theappearance of the exposed surface.

The low-cost mass production of articles similar to the one describedabove requires that the fire-resistant composition have a plurality ofdesirable characteristics. Obviously, it must be resistant to wear andmoisture when cured and be capable of holding a consistant opaque colorto hide the grain of the plywood. Additionally, the composition must gelquickly and set to avoid sagging and must also cure to hardness quicklyto permit handling. This curing process should take place at roomtemperature. Also, the various components should desirably be of lowvolatility and free of noxious odor during both mixing and curing.

Equally important in this case is the reaction of the cured compositionto flames and high temperature. Obviously, it must not add to the flamesand, in addition, it should protect from high temperature and ignitionthe substrate which, in this case, is wood. The latter effect isaccomplished by self-expansion or puffing of the composition to manytimes its cure thickness with the resulting creation of a foam-thermalbarrier. This property of foaming or puffing with exposure to heat iscalled intumescence. Also, exposure to intense heat should not cause thecomposition to give off undesirable smoke or odor.

The invention involves a combination of compounds which, when added to abatch of a suitable monomer, combine synergistically to impart not onlydesirable curing and physical properties but also fire resistance andintumescence. The character of the invention should be made clear by thefollowing examples. Unless otherwise noted, compositions are expressedin parts by weight. The invention also involves various useful forms ofthe composition in symbiotic combination with compatable substrates,such as wood, plastic and reinforced plastic composites.

EXAMPLE 1

The first step in the reduction to practice was the preparation of themixture of monomers and flame-retardant chlorinated organic material.The formula W18-222-1 was as follows:

                          %       g                                               ______________________________________                                        Hydroxy propylacrylate monomer (CX-2383,                                       Dow Chemical Company)  17.95     718                                         Methyl methacrylate monomer                                                    (Union Carbide Corp.)  17.95     718                                         Chlorez 700AX (Dover Chemical Co.)                                             chlorinated paraffin (70% chlorine)                                                                  63.50     2540                                        Super Airout (Isochem Resins Co.)                                              (an air release agent comprising a silane                                     modified product of a silicone reacted                                        with a tallate)        0.10      4                                           wetting agent           0.50      20                                                                  100.00    4000                                        ______________________________________                                    

The ingredients were added, in the order shown to a 1-gallonfriction-top can, with mechanical agitation.

The second step was the establishment of a suitable curing system whichwill give an initial cure at room temperature without application ofheat. The following systems were tried:

                       W18-222-                                                                      2     3       4                                            ______________________________________                                        W18-222-1            100 g.  100 g.  100 g.                                   2,4-Pentanedione (Union Carbide                                                Corp.)              0.4     --      --                                       Lupersol PDO (50% t-butyl peroctoate)                                          (Lucidol Division, Pennwalt Corp.)                                                                2       --      --                                       Luperco ANS-50 (50% benzoyl peroxide)                                          Lucidol Division, Pennwalt Corp.)                                                                 --      0.70    0.70                                     Cobalt Catalox 12% (Ferro Chemical                                             Division, Ferro Corporation)                                                  12% coblat catalytic paint dryer                                                                  0.4     --      --                                       N,N-Dimethyl-p-toluidine (Naftone,                                             Inc.)               --      0.14    --                                       N,N-Dimethylaniline (American                                                  Cyanamide Company)  --      --      0.14                                     ______________________________________                                    

In each experiment, the ingredients were added, in the order shown, to a6-oz. plastic-coated paper hot-drink cup with hand mixing with a woodenspoon after each addition. The timing for gel time was begun at the timeof mixing in of the cobalt or amine promoter. Each cup was allowed tostand at room temperature (about 72°F) without external heating.Experiment W18-222-2 began to gel in 30 minutes; W18-222-3 in 5 to 8minutes; W18-222-4 in about 20 minutes. Of the three systems tested, thedimethyl-p-toluidinebenzoyl peroxide (W18-222-3) was considered mostsuitable.

An antimony oxide masterbatch, W18-222-5, was prepared by the additionof 400 g. of Thermogard S (M & T Chemicals, Inc.) to 400 g. of monomermixture W18-222-1 with mechanical agitation. The Thermogard-monomer mixwas passed once through a laboratory hand homogenizer (Scientific GlassApparatus Co., Inc., 1969 Catalog No. H-2585).

The next step was the preparation of a cast cured panel for evaluationof flame-retardant properties. The formula for this preparation(W18-222-6) was as follows:

                                g                                                 W18-222-1 monomer mix       600                                               W18-222-5 antimony oxide masterbatch                                                                      76                                                Industrial ground gypsum (United States Gypsum Co.)                                                       825                                               Iron oxide                  15                                                Luperco ANS-50 (50% benzoyl peroxide)                                                                     4.2                                                (Lucidol Division, Pennwalt Corp.)                                           N,N-Dimethyl-p-toluidine (Naftone, Inc.)                                                                  0.60                                          

The ingredients were added, in the order shown, to a one-quartfriction-top can with mechanical agitation. Immediately following themixing in of the dimethyl-p-toluidine, the mix was poured into a steelmold 223/4 inches long, 3 9/16 inches wide and 1 inch deep, lined with0.5-mil Mylar film. The mix was smoothed out to form a layer 1/4 inchdeep. Gelation occurred without application of heat in 15 to 20 minutesat 80°F. The panel appeared to be well cured after overnight standing,as judged by qualitative surface hardness. After 3 days, the Barcolhardness was 10-20 as determined with the Barcol Impressor(Barber-Colman Co., Model GYZJ 934-1).

The F.S.R. of the cast panel was determined by a modification of themethod described in Special Report No. 6090 entitled Use of a SmallFlame Tunnel in the Laboratory Evaluation of Flame Spread Rating, datedMay 5, 1964, prepared by H. L. Vandersall of Monsanto Company. The FlameTunnel was constructed in accordance with the descriptions on page III-2and in FIGS. 1 and 2 of the Appendix of the above report and is known asa "Two-Foot Tunnel". It should be noted that this two-foot tunnel setupis generally equivalent to the official 25 ft. tunnel used in thestandard Steiner Tunnel Test (A.S.T.M. E 84) (see Example 8). The fuelsource for the Type 3-900 Fisher burner flame source was bottled propanegas (suggested as a modification on page V-1 of the above report). Thedetermination of F.S.R. was made in accordance with the proceduredescribed on pages IV-1 through IV-4 of the above report, with thefollowing modifications:

1. Thermocouples for measuring insulative ability were not used.

2. The position of the flame front was recorded every 30 seconds for thefirst 4 minutes, and every 60 seconds for an additional 6 minutes.

The maximum flame length (average of the three highest values obtainedduring the first four minutes) was 10 inches; the maximum flame lengthduring the last six minutes was 101/2 inches. The F.S.R. was calculatedfrom the above data, together with calibration data obtained with thesame equipment and by the same procedure using asbestos and red oakstandards. The F.S.R. for the W18-222-6 test panel calculated asdescribed above was 17.5. No afterflaming was observed, and theafterglowing (length of time after all flaming ceases but whilered-glowing embers are still visible) was 10 seconds. The char lengthwas 121/2 inches. The foam thickness at the point of flame impingementon the panel was about 12 millimeters (original panel thickness about 6millimeters). The results of the F.S.R. tests show that the compositiondescribed is capable of being fabricated into a panel with excellentflame-retardant properties, and that a successful reduction to practiceof the invention has been achieved.

EXAMPLE 2

In order to establish a basis of comparative flame resistance, acomposition presented in British Patent No. 1,157,436, published on July9, 1969, and purporting to contain a "flameproofing agent", was set upas a standard in the above-mentioned test.

The material was formed in two syrups as follows:

    SYRUP A                                                                       Methyl methacrylate monomer                                                                            70.                                                  Methyl methacrylate polymer                                                                            30.                                                  Ethylene glycol dimethacrylate                                                                         1.5                                                  Dimethyl-p-toluidine (DMPT)                                                                            .5                                                                            101.9                                                SYRUP B                                                                       Tricresyl phosphate      30.                                                  Tris (2,3-dichloropropyl) phosphate                                            (Fyrol FR-2)            10.                                                  Unichlor 70 AX (Chlorinated Paraffin)                                                                  40.                                                  ANS-50 (benzoyl peroxide paste)                                                                        2.                                                                            82.                                              

The syrups were then combined (230 parts by wt. of Syrup A and 100 partsby wt. of Syrup B) to form a 4 inches × 23 inches laminate with one plyof 11/2 oz. glass mat. The material gelled in 15 to 18 minutes and had aF.S.R. of 100+, much higher than that of the composition of Example 1.

EXAMPLE 3

A mixture similar to Example 2 was filled with antimony oxide (a knownflame retardant) and hydrated alumina.

    ______________________________________                                        Syrup A                 300.                                                  Syrup B                 135.                                                  KR-LTS antimony oxide (Harshaw)                                                                       21.5                                                  C-31 coarse hydrated alumina (Alcoa)                                                                  500.                                                                          956.                                                  ______________________________________                                    

This composition was cast into a 4 inches × 23 inches sheet, and gelledin 15 to 18 minutes. It had a F.S.R. of 70, much higher than thecomposition of Example 1.

EXAMPLE 4

The effect of filler addition on the mixture of Example 1 was examined.A base resin, similar to that of Example 1,

    Hydroxy propylacrylate monomer                                                                         18.0                                                 Methyl methacrylate monomer                                                                            27.0                                                 Chlorinated paraffin (70% chlorine)                                                                    55.0                                             

was mixed with filler to form:

    Base resin              100.                                                  Antimony oxide          5.5                                                   Zinc oxide              20.0                                                  Hydrated alumina        150.0                                                 50% benzoyl peroxide paste (ANS-50)                                                                   1.0                                                   N,N-Dimethyl-p-toluidine                                                                              0.2                                               

The result was a mixture that gelled at 75°F in 5 to 8 minutes, had aBarcol of 40 and a F.S.R. of 25 in a 2' tunnel.

EXAMPLE 5

In order to examine further the effect of inorganic fillers, a basicresin (No. 8248),

    Hydroxy propylacrylate                                                                            18.                                                       Methyl methacrylate 27.                                                       Unichlor 70 AX      55.                                                       Emersol 233 (oleic acid)                                                                          .5                                                        Super Airout        .1                                                        Hydroquinone        .009                                                                          100.                                                  

was filled with various fillers.

    ______________________________________                                        No. 8248 resin       600.                                                     KR-LTS antimony oxide                                                                              33.                                                      No. 17 Zinc oxide    120.                                                     Ground gypsum        700.                                                     ANS-50 BP paste      6.                                                       Dimethyl-p-toluidine (DMPT)                                                                        1.2                                                                           1460.2                                                   ______________________________________                                    

This mixture gelled in 8 minutes, and had a F.S.R. of 17.5. It gave offa trace of smoke, had some puff, and had a slight sag.

EXAMPLE 6

    No. 8248 resin     600.                                                       KR-LTS antimony oxide                                                                            33.                                                        No. 17 Zinc oxide  120.                                                       Ground bauxite     600.                                                       ANS-50 BP paste    6.                                                         DMPT               1.2                                                                           1360.2                                                 

This mixture gelled in 12 to 13 minutes and had a F.S.R of 25. It gaveoff more smoke than Example 4 containing hydrated alumina.

EXAMPLE 7

    No. 8248 resin         600.                                                   KR-LTS antimony oxide  33.                                                    No. 17 Zinc oxide      120.                                                   No. 1 terra alba (Purified gypsum                                              from U.S. Gypsum Co.) 600.                                                   ANS-50 BP paste        6.                                                     DMPT                   1.2                                                                           1360.2                                             

This mixture gelled in 10 to 11 minutes with very bad sag (no backing).The F.S.R. was 8.8, and more smoke was generated than Example 1.

EXAMPLE 8

    No. 8248 resin     39.50                                                      Vanadium (6% solution)                                                                           .08                                                        Manganese Naphthenate                                                          (6% solution)     .2                                                         2,4-Pentanedione   .2                                                         No. 17 Zinc oxide  7.9                                                        KR-LTS antimony oxide                                                                            2.17                                                       Coarse hydrated alumina                                                                          50.                                                        Cumene hydroperoxide                                                                             .6                                                                            100.                                                   

This mixture had a viscosity of 8.000 c.p.s. after 6 minutes and gelledat 15 to 18 minutes, both at 72°C. It had a density of 15.35lbs./gallon. It was cast onto regular construction-grade plywood andsprinkled before gelation with 3/4 inch granite roofing chips. TheF.S.R. was 6 and the smoke was undetectable when tested in the 2 foottunnel. It should be noted that this same material was run in a 25 foottunnel which is the official setup for the Steiner Tunnel Test (A.S.T.M.E 84), resulting in a F.S.R. of 2.5 and the smoke generated was zero.This slightly better result not only shows the general equivalence ofthe two setups, but also suggests that the 2 foot tunnel test issomewhat more severe.

EXAMPLE 9

An essentially unfilled mixture consisting of:

    No. 8248 resin      100.                                                      Van. 6%             .2                                                        Mang. 6%            .5                                                        2,4-Pentanedione    .5                                                        Cumene hydroperoxide                                                                              1.5                                                                           102.7                                                 

was formed into a laminate with two plies of 11/2 oz. glass mat. TheF.S.R. is 100.

EXAMPLE 10

The above mixture was formed with antimony oxide as follows:

    No. 8248 resin       400.                                                     Van. 6%              .4                                                       Mang. 6%             1.                                                       2,4-Pentanedione     2.                                                       KR-LTS antimony oxide                                                                              20.                                                      Cumene hydroperoxide 6.                                                                            429.4                                                

and formed into a laminate with 11/2 oz. glass mat. The F.S.R. was 41which demonstrates the fire-retarding qualities of antimony oxide.

EXAMPLE 11

Following the same line of thought used in Examples 9 and 10, themixture was filled with hydrated alumina.

    ______________________________________                                        No. 8248 resin         600.                                                   KR-LTS antimony oxide  33.                                                    No. 17 Zinc oxide      120.                                                   C-31 coarse hydrated alumina                                                                         900.                                                   ANS-50 BP paste        6.                                                     DMPT                   1.2                                                                           1660.2                                                 ______________________________________                                    

This mixture gelled in 25 minutes. It had a F.S.R. of 8.8, gave off nosmoke, and did not sag.

EXAMPLE 12

In this case, terra alba was used as the filler.

    ______________________________________                                        No. 8248 resin       600.                                                     KR-LTS antimony oxide                                                                              33.                                                      No. 17 Zinc oxide    120.                                                     No. 1 terra alba     500.                                                     ANS-50 BP paste      6.                                                       DMPT                 .9                                                                            1259.9                                                   ______________________________________                                    

The liquid mixture had a density of 14.5 lbs./gallon and gelled in 12minutes. The F.S.R. was 12, but the material sagged and smoked badly,and smoldered after the flame died.

EXAMPLE 13

In order to encourage cross-linking and thus a more rigid panel, adimethacrylate was added.

    ______________________________________                                        No. 8248 resin         600.                                                   KR-LTS antimony oxide  33.                                                    No. 17 Zinc oxide      120.                                                   No. 1 terra alba       500.                                                   Ethylene glycol dimethacrylate                                                                       30.                                                    ANS-50 BP paste        6.                                                     DMPT                   .9                                                                            1289.9                                                 ______________________________________                                    

The more rigid panel gelled in 10 to 12 minutes, had a F.S.R. of 25, hadno sag or puff, and generated more smoke than Example 4.

EXAMPLE 14

To make a lightweight panel, glass bubbles were added.

    ______________________________________                                        No. 8248 resin       600.                                                     KR-LTS antimony oxide                                                                              33.                                                      No. 17 Zinc oxide    120.                                                     No. 1 terra alba     400.                                                     3M Glass bubbles     60.                                                      ANS-50               6.                                                       DMPT                 .9                                                                            1219.9                                                   ______________________________________                                    

The liquid had a density of 10.74 lbs./gallon and gelled in 10 to 12minutes. It had a F.S.R. of 17, slight sag, and generated more smokethan Example 4.

EXAMPLE 15

The mixture of Example 11 was cast onto 3/4 inch fire-resistant plywoodto a thickness of about one-sixteenth inch. 1/4 inch diameter stoneswere spread on top and the resin was allowed to cure. The F.S.R. was111/2.

EXAMPLE 16

The mixture of Example 13 was cast onto 3/4 inch fire-resistant plywoodto a thickness of about one-sixteenth inch. 1/4 inch diameter stoneswere spread on top and the resin was allowed to cure. The F.S.R. was 6.

EXAMPLE 17

In this case, ethyl acrylate replaced hydroxy propylacrylate. The resin(25-51-1) was prepared as follows:

    Ethyl acrylate    18.                                                         Methyl methacrylate                                                                             27.                                                         Unichlor 70 AX    55.                                                         Emersol 233       .5                                                          Super Airout      .1                                                                            100.                                                    

A mixture analogous to that of Example 11 was formed.

    ______________________________________                                        25-51-1 resin         39.5                                                    Van. 6%               .08                                                     Mang. Nap. 6%         .2                                                      2,4-Pentanedione      .2                                                      No. 17 Zinc oxide     7.9                                                     KR-LTS antimony oxide 2.17                                                    C-31 coarse hydrate alumina                                                                         50.0                                                                          100.                                                    ______________________________________                                    

This material had a F.S.R. of 25, and cured very slowly, gelling after30 minutes. It also had a relatively low heat distortion temperature.

EXAMPLE 18

In this case, the hydroxy propylacrylate of Example 11 was replaced bynormal-butyl acrylate,

                           21-51-2                                                N-Butyl acrylate       18.                                                    Methyl methacrylate    27.                                                    Unichlor 70 AX         55.                                                    Emersol 233            .5                                                     Super Airout           .1                                                                            100.                                                   25-51-2 resin          39.5                                                   Van. 6%                .08                                                    Mang. Nap. 6%          .2                                                     2,4-Pentanedione       .2                                                     No. 17 Zinc oxide      7.9                                                    KR-LTS antimony oxide  2.17                                                   C-31 coarse hydrated alumina                                                                         50.0                                                                          100.                                               

As with Example 17, the cure of this mixture was very slow, with geloccuring after 25 minutes. The F.S.R. was 25 and heat distortiontemperature was very low.

EXAMPLE 19

Here, ethyl acrylate was substituted for the methyl methacrylate. TheF.S.R. was 30.

    ______________________________________                                        Resin No. 7670            Wt.%                                                ______________________________________                                        Ethyl acrylate     24.75      19.92                                           Hydroxy propylacrylate                                                                           24.87      20.02                                           Chlorez 70 AX (chlorinated                                                    hydrocarbon paraffin)                                                                            74.63      60.06                                                              124.25     100.                                            No. 7670 resin     250        42.7                                            Antimony oxide grind 50%                                                                         30         5.1                                             Ground gypsum      305        52.2                                                               585        100.                                            ______________________________________                                    

EXAMPLE 20

In another attempt without methyl methacrylate, the mixture below wascured with 0.66% t-butyl peroctoate, had a F.S.R. of 20 and gave off nosmoke.

    ______________________________________                                        Hydroxy propylacrylate                                                                          200.        19.42                                           Chlorowax 70      300.        29.14                                           Therm. S (antimony oxide)                                                                       30.         2.91                                            Ground gypsum     500.        48.53                                                             1030.       100.                                            ______________________________________                                    

EXAMPLE 21

In this experiment, a composition is prepared with a high concentrationof chlorinated hydrocarbon. The mixture gelled in 15 to 20 minutes andhad a F.S.R. of 20.5. It burned with a trace of smoke and some odor.

    ______________________________________                                        No. 7747 Resin                                                                ______________________________________                                        Hydroxy propylacrylate         17.95                                          Methyl methacrylate            17.95                                          Chlorez 70 AX (chlorinated                                                    hydrocarbon)                   63.50                                          Super Airout                   .10                                            wetting agent                  .50                                                                           100.                                           No. 7747 resin    600          39.85                                          Antimony oxide grind 50%                                                                        76           5.05                                           Ground gypsum     825          54.80                                          DMPT              .6           .04                                            ANS-50            4.2          .28                                                              1505.8       100.02                                         ______________________________________                                    

EXAMPLE 22

Conversely to Example 21, the amount of chlorinated hydrocarbon wasreduced to zero. The surface cured very poorly, remaining tacky for along period. The F.S.R. was 25, but a bad sag was noted. The burningproduced sparks, but no smoke, little char and almost no odor.

    ______________________________________                                                                  Wt.%                                                ______________________________________                                        Hydroxy Propylacrylate                                                                             200.       13.08                                         Methyl methacrylate  300.       19.62                                         C-31 coarse          1000.      65.40                                         Oncor 75RA (N L Industries, Inc.)                                             (an antimony trioxide                                                          based fire retardant)                                                                             15.        .98                                           Cadox 40-E 40% Benzoyl Peroxide                                               in dibutyl phthalate 12.5       .81                                           DMPT                 2.         .13                                                                1529.5     100.02                                        ______________________________________                                    

EXAMPLE 23

In a slightly different mixture, made without chlorinated hydrocarbon,the material gelled in 15 to 18 minutes and cured with a hard surface.The F.S.R. was 25, producing no smoke but many sparks.

    ______________________________________                                                                  Wt. %                                               ______________________________________                                        Methyl methacrylate                                                                             225.          24.46                                         Hydroxy propylacrylate                                                                          75.           8.15                                          E/G dimethacrylate                                                                              6.            .65                                           C-31 coarse       600.          65.2                                          Aerosil           7.            .76                                           ANS-50            6.            .65                                           DMPT              1.2           .13                                                             920.2         100.                                          ______________________________________                                    

EXAMPLE 24

A mixture was prepared without hydroxy propylacrylate. The materialpoured well, had a F.S.R. of 60 and flaked off of substrate during flametest.

    ______________________________________                                                                        Wt.%                                          Methyl methacrylate                                                                            200.           19.265                                        Unichlor 70 AX   200.           19.265                                        E/G dimethacrylate                                                                             20.            1.926                                         KR-LTS           10.            .964                                          C-31 coarse      600.           57.80                                         Cadox 40-E       7.             .675                                          DMPT             1.6            .015                                                           1038.6         99.910                                        ______________________________________                                    

EXAMPLE 25

In developing the role of hydroxy propylacrylate in flame-retardance,this mixture was prepared with a lower than normal concentration of thehydroxy propylacrylate. The material gelled in 8 minutes and cured well.It had a F.S.R. of 30, no sag and good puff.

    ______________________________________                                        Methyl methacrylate                                                                              70.           13.38                                        Chlorowax          130.          24.85                                        Hydroxy propylacrylate                                                                           8.75          1.67                                         E/G dimethacrylate 8.75          1.67                                         Oncor 75RA         12.8          2.44                                         C-31 coarse        290.          55.4                                         Cadox 40-E         2.62          .5                                           DMPT               .28           .05                                                             523.20        99.96                                        ______________________________________                                    

EXAMPLE 26

The remaining tests (Examples 26-35) were all carried out with a plywoodbacking as the substrate. The plywood was pretreated with a tiecoat ofpolyester. The polyester was allowed to partially cure before themixtures were applied. Furthermore, these remaining examples wereexecuted as a group with great care taken to eliminate unintendedvariation in parameters.

A mixture without the stones gelled in 16 to 18 minutes. It had a F.S.R.of 12, good adhesion and protected the wood from charring.

    ______________________________________                                        No. 8248 resin        600.                                                    Van. 6%               1.2                                                     Mang. 6%              3.0                                                     2,4-Pentanedione      3.0                                                     KR-LTS                33.                                                     C-31 coarse           762.                                                    Cumene hydroperoxide  9.                                                      No. 17 Zinc oxide     120.                                                                          1531.2                                                  ______________________________________                                    

EXAMPLE 27

The above mixture was then made up without antimony oxide. It gelled in18 to 20 minutes, had a F.S.R. of 25, had good adhesion and protectedwood from charring.

    ______________________________________                                        No. 8248 resin        600.                                                    Van. 6%               1.2                                                     Mang. 6%              3.                                                      2,4-Pentanedione      3.                                                      No. 17 Zinc oxide     120.                                                    C-31 coarse           762.                                                    Cumene hydroperoxide  9.                                                                            1498.2                                                  ______________________________________                                    

EXAMPLE 28

The antimony oxide was replaced by Firebrake ZB (zinc borate). Theresulting mixture gelled in 16 to 18 minutes. It had a F.S.R. of 18, hadgood adhesion and protected the wood from charring.

    ______________________________________                                        No. 8248 resin         600.                                                   Van. 6%                1.2                                                    Mang. 6%               3.                                                     2,4-Pentanedione       3.                                                     No. 17 Zinc oxide      120.                                                   Firebrake ZB           33.                                                    C-31 course            762.                                                   Cumene hydroperoxide   9.                                                                            1531.2                                                 ______________________________________                                    

EXAMPLE 29

A mixture was then prepared without either zinc oxide or antimony oxide.The resulting material gelled in 12 to 14 minutes, had a F.S.R. of 30,had very poor adhesion and allowed wood to become charred.

    ______________________________________                                        No. 8248 resin         600.                                                   Van. 6%                1.2                                                    Mang. 6%               3.                                                     2,4-Pentanedione       3.                                                     C-31 coarse            762.                                                   Cumene hydroperoxide   9.                                                                            1378.2                                                 ______________________________________                                    

EXAMPLE 30

The mixture was then prepared with antimony oxide, but no zinc oxide.The gel formed in 30 minutes, and the cured product had a F.S.R. of 25,had good adhesion, and protected the wood. The puff was not as good asExample 26.

    ______________________________________                                        No. 8248 resin         600.                                                   Van. 6%                1.2                                                    Mang. 6%               3.0                                                    2,4-Pentanedione       3.0                                                    KR-LTS                 33.                                                    C-31 coarse            762.                                                   Cumene hydroperoxide   9.                                                                            1411.2                                                 ______________________________________                                    

EXAMPLE 31

A mixture without zinc oxide, but with Firebrake ZB (zinc borate),gelled in 20 to 23 minutes, had a F.S.R. of 18, protected the wood, andhad good adhesion.

    ______________________________________                                        No. 8248 resin         600.                                                   Van. 6%                1.2                                                    Mang. 6%               3.0                                                    2,4-Pentanedione       3.0                                                    Firebrake ZB           33.                                                    C-31 coarse            762.                                                   Cumene hydroperoxide   9.                                                                            1411.2                                                 ______________________________________                                    

EXAMPLE 32

Hydroxy butyl acrylate (HBA) was substituted for the hydroxypropylacrylate. The resulting mixture gelled in 10 to 12 minutes, had aF.S.R. of 9, and had good adhesion. It also had good puff and protectedthe wood. The uncured monomer was extremely smelly, however. Theadhesion to the wood was fair.

    ______________________________________                                        Batch 25-59-2                                                                 MMA                     270                                                   Unichlor                55                                                    Super Airout            1                                                     Emersol                 5                                                     Hydroquinone            0.09                                                  25-59-2 (MMA/Unichlor)  246.                                                  24-236-1 HBA            54.                                                   Van. 6%                 .6                                                    Mang. 6%                1.5                                                   2,4-Pentanedione        1.5                                                   KR-LTS                  16.5                                                  No. 17 Zinc oxide       60.                                                   C-31 coarse             381.                                                  Cumene hydroperoxide    4.5                                                                           765.6                                                 ______________________________________                                    

EXAMPLE 33

Here the hydroxy propylacrylate was replaced by Cellosolve acrylate(ethylene glycol monoethyl ether acrylate). The uncured mixture gave offa very strong odor and gelled in 10 to 11 minutes. The cured materialhad a F.S.R. of 12, exhibited very good adhesion to the wood, andprotected the wood from char. It also had a good puff and gave off nosmoke.

    ______________________________________                                        25-59-2 (MMA/Unichlor)  246.                                                  Cellosolve acrylate     54.                                                   Van. 6%                 .6                                                    Mang. 6%                1.5                                                   2,4-Pentanedione        1.5                                                   KR-LTS                  16.5                                                  No. 17 Zinc oxide       60.                                                   C-31 coarse             381.                                                  Cumene hydroperoxide    4.5                                                                           765.6                                                 ______________________________________                                    

EXAMPLE 34

In this example, the hydroxy propylacrylate was replaced by hydroxyethylacrylate. The resulting material gelled in 3 to 4 minutes, had aF.S.R. of 15, and protected the wood. It had only fair adhesion.

    ______________________________________                                        Batch 25-59-1                                                                 ______________________________________                                        MMA                   270                                                     HEA                   180                                                     Unichlor              55                                                      Super Airout          1                                                       Emersol               5                                                       Hydroquinone          0.09                                                    25-59-1 (18% HEA)     300.                                                    Van. 6%               .6                                                      Mang. 6%              1.5                                                     2,4-Pentanedione      1.5                                                     KR-LTS                16.5                                                    No. 17 Zinc oxide     60.                                                     C-31 coarse           381.                                                    Cumene hydroperoxide  4.5                                                                           765.6                                                   ______________________________________                                    

EXAMPLE 35

Here, the hydroxy propylacrylate was replaced by diacetone acrylamide.The resulting material gelled in 5 to 6 minutes and had a F.S.R. of 12.It gave a good puff that was only half charred and the adhesion wasgood.

    ______________________________________                                        25-59-2 (MMA/Unichlor) 246.                                                   Diacetone acrylamide   54.                                                    Van. 6%                .6                                                     Mang. 6%               1.5                                                    2,4-Pentanedione       1.5                                                    KR-LTS                 16.5                                                   No. 17 Zinc oxide      60.                                                    C-31 coarse            381.                                                   Cumene hydroperoxide   4.5                                                                           765.6                                                  ______________________________________                                    

EXAMPLE 36

In an attempt to discover reasonable replacements for MMA, a batch25-115-1 was prepared involving styrene, and combined as shown below. A70 mil. casting of the resulting material was made on mylar, backed upwith 2 plies of 11/2 oz. glass mat and a rigid polyester resin. Thematerial gelled in 45 minutes and was very slow in cure. The resultingstructure had a F.S.R. of 35, no intumescence, slight sag, and mediumsmoke generation.

    ______________________________________                                        Batch 25-115-1                                                                ______________________________________                                        Styrene monomer         270.                                                  Hydroxy propylacrylate  180.                                                  Unichlor 70 AX          550.                                                  Super Airout            1.                                                    Emersol 233             5.                                                    Hydroquinone            0.09                                                                          1006.                                                 W25-115-1               300.                                                  Antimony oxide KR-LTS   16.5                                                  No. 17 Zinc oxide       60.                                                   C-31 coarse hydrated alumina                                                                          381.                                                  6% Vanadium Ten-Cem (Mooney)                                                                          0.6                                                   6% Manganese Naphthenate (Ferro)                                                                      1.5                                                   2,4-Pentanedione        1.5                                                   Cumene hydroperoxide    4.5                                                                           765.6                                                 ______________________________________                                    

EXAMPLE 37

In this experiment, acrylamide was examined in the mixture shown below.The V-pyrol was required to dissolve the acrylamide. A 70 mil. castingwas made on mylar film, back with 2 plies of 11/2 oz. glass mat and aflame retardant resin from Diamond Shamrock Corp. The material gelled in3 to 4 minutes but remained soft and cheezy after overnite cure.

The cured structure had a F.S.R. of 30, no intumescence, slight sag andheavy smoke.

    ______________________________________                                        Acrylamide               50.                                                  GAF V-pyrol (N-vinyl-2-pyrrolidone)                                                                    115.                                                 Unichlor 70 AX           170.                                                 6% Van. Ten-Cem          0.6                                                  6% Mang. Naph.           1.5                                                  2,4-pentanedione         1.5                                                  Antimony oxide KR-LTS    16.5                                                 No. 17 Zinc oxide        60.                                                  C-31 coarse hydrated alumina                                                                           381.                                                 Cumene hydroperoxide     4.5                                                                           800.6                                                ______________________________________                                    

EXAMPLE 38

The mixture in Example 35 was used as a gel coat and cast on a mold atthe thickness of 70 mils. After gelling and partially curing, the gelcoat was layed up with a general purpose rigid unsaturated polyesterresin reinforced with fiberglass mat giving a laminate of approximatelyone-eigth inch. After curing, the laminate was tested for fireresistance in the 2 foot tunnel with the flame on the gel coat side. TheF.S.R. was 18, with good puff and no smoke.

EXAMPLE 39

The experiment in Example 38 was repeated but this time using afire-resistant back-up resin claimed to have an F.S.R. of 25. In thefire test on this laminate in the 2 foot tunnel the gel coat side wasagain exposed to the flame. The results were the same as with thegeneral purpose back-up resin, F.S.R. 18, good puff and no smoke.

EXAMPLE 40

In this experiment Dechlorane Plus (non paraffin) (Hooker Chemical Co.)was substituted for the Unichlor 70-AX chlorinated paraffin in the gelcoat from Example 35. The fire-resistant back-up resin was used as inExample 39. The F.S.R. was 35 and there was considerable smoke.

EXAMPLE 41

In this experiment Chlorowax 50 (Diamond Shamrock chlorinated paraffincontaining 50% chlorine) was used in place of Unichlor 70-AX in the gelcoat from Example 35. The F.S.R was 41 with medium smoke.

EXAMPLE 42

In this experiment Firemaster RBF-1 was used in place of the Unichlor70-AX in the gel coat from Example 35. RBF-1 is a liquid brominatedorganic compound of Michigan Chemical Corp. The F.S.R. was 30, there waslight smoke, and good adhesion.

EXAMPLE 43

In this experiment Firemaster BP-6 (Michigan Chemical Corp.) was used inplace of the Unichlor 70-AX in the gel coat from Example 35. The F.S.R.was 30 and there was heavy white smoke.

While it will be apparent that the illustrated embodiments of theinvention herein disclosed are well calculated adequately to fulfill theobjects and advantages primarily stated, it is to be understood that theinvention is susceptible to variation, modification, and change withinthe spirit and scope of the subjoined claims.

The invention having been thus described, what is claimed as new anddesired to secure by Letters Patent is:
 1. A fire-resistant productcomprising a flammable substrate and a layer of fire-retardant materialbonded to the surface of the substrate, said material resulting frompolymerization of a mixture comprising from 4-50 wt.% of a first monomerchosen from the group consisting of hydroxy ethylacrylate, hydroxypropylacrylate, hydroxy butylacrylate, ethylene glycol monoethyl etheracrylate and diacetone acrylamide, from 0-50 wt.% of an alkylmethacrylate monomer, and from 30-70 wt.% of a chlorinated paraffincontaining from 40-75 wt.% chlorine and including a heat intumescentssubstance.
 2. A first-resistant product as recited in claim 1, whereinthe first monomer is hydroxy propylacrylate.
 3. A fire-resistant productas recited in claim 1, wherein an antimony containing material is acomponent of said mixture.
 4. A fire-resistant product as recited inclaim 1, wherein ground gypsum, also known as hydrated calcium sulphate,is a component of said mixture.
 5. A fire-resistant product as recitedin claim 1, wherein hydrated alumina is a component of said mixture. 6.A fire-resistant product as recited in claim 1, wherein ground bauxiteis a component of said mixture.
 7. A fire-resistant product as recitedin claim 1, wherein a peroxide catalyst is a component of said mixture.8. A fire-resistant product as recited in claim 1, wherein an aminepromoter is a component of said mixture.
 9. A fire-resistant product asrecited in claim 1, wherein said mixture includes a catalyst systemcomprising a solution containing vanadium, a solution containingmanganese, 2,4-pentanedione, and cumene hydroperoxide.
 10. Afire-resistant product as recited in claim 3, wherein the antimonycontaining material is antimony oxide.
 11. A fire-resistant product,comprisinga. a substrate having high strength characteristics, and b. aprotective layer bonded to the surface of the substrate, the layer beingcomprised ofi. a first monomer chosen from the group consisting ofhydroxy ethylacrylate, hydroxy propylacrylate, hydroxy butylacrylate,ethylene glycol monoethyl ether acrylate, diacetone acrylamide, andcombinations thereof, ii. a chlorinated paraffin containing 40-75 wt.%of chlorine, iii. a hydrated mineral filler, iv. an inorganic flameretardant, and v. a catalyst-promoter system to cure the mixture.
 12. Afire-resistant product as recited in claim 11, wherein the substrate isa fiberglass reinforced plastic on which the protective layer is bondedas a gel coat and the protective layer includes a second monomer.
 13. Afire-resistant product as recited in claim 11, wherein the inorganicflame retardant is a combination of antimony oxide and zinc oxide.